The process produces at least one fuel from at least two different types of renewable feedstocks including biomass derived pyrolysis oil and the triglycerides and free fatty acids found in plant and animal oils fats and greases. The two different types of renewable feedstocks are co-processed with at least one paraffin rich component produced from the triglycerides and free fatty acids found in plant and animal oils fats and greases and with at least one cyclic rich component produced from a biomass derived pyrolysis oil. The effluent containing at least one paraffin rich fuel component and at least one aromatic rich fuel component is useful as at least one fuel or fuel blending component. The fuel, fuel additives, or blending components generated may include those in the gasoline boiling point range, the diesel boiling point range, and or the aviation boiling point range.
As the demand for gasoline, diesel fuel, and aviation fuel increases worldwide there is increasing interest in sources other than petroleum crude oil for producing these fuels. One such source is what has been termed renewable feedstocks. One type of renewable feedstocks include, but are not limited to, plant oils such as corn, rapeseed, canola, soybean and algal oils, animal fats such as inedible tallow, fish oils and various waste streams such as yellow and brown greases and sewage sludge. The common feature of these feedstocks is that they are composed of glycerides and Free Fatty Acids (FFA). Both of these compounds contain aliphatic carbon chains having from about 8 to about 24 carbon atoms. The aliphatic carbon chains in the triglycerides or FFAs can also be mono-, di- or poly-unsaturated. Some of the glycerides from the renewable sources may be monoglycerides or diglycerides instead of or in addition to the trigylcerides. This type of feedstock is employed to generate the paraffinic portion of a fuel.
There are reports in the art disclosing the production of hydrocarbons from oils. For example, U.S. Pat. No. 4,300,009 discloses the use of crystalline aluminosilicate zeolites to convert plant oils such as corn oil to hydrocarbons such as gasoline and chemicals such as para-xylene. U.S. Pat. No. 4,992,605 discloses the production of hydrocarbon products in the diesel boiling point range by hydroprocessing vegetable oils such as canola or sunflower oil. Finally, US 2004/0230085 A1 discloses a process for treating a hydrocarbon component of biological origin by hydrodeoxygenation followed by isomerization.
The generation of the cyclic rich component of the fuel employs a process for obtaining a cyclic rich component from biomass. More particularly, this process relates to the treatment of pyrolysis oil produced from the pyrolysis of biomass to produce fuel or fuel blending or additive components. As discussed above, renewable energy sources are of increasing importance. They are a means of reducing dependence on petroleum oil and provide a substitute for fossil fuels. Also, renewable resources can provide for basic chemical constituents to be used in other industries, such as chemical monomers for the making of plastics. Biomass is a renewable resource that can provide some of the needs for sources of chemicals and fuels.
Biomass includes, but is not limited to, lignin, plant parts, fruits, vegetables, plant processing waste, wood chips, chaff, grain, grasses, corn, corn husks, weeds, aquatic plants, hay, paper, paper products, recycled paper and paper products, and any cellulose containing biological material or material of biological origin. Lignocellulosic biomass, or cellulosic biomass as used throughout the remainder of this document, consists of the three principle biopolymers cellulose, hemicellulose, and lignin. The ratio of these three components varies depending on the biomass source. Cellulosic biomass might also contain lipids, ash, and protein in varying amounts. The economics for converting biomass to fuels or chemicals depend on the ability to produce large amounts of biomass on marginal land, or in a water environment where there are few or no other significantly competing economic uses of that land or water environment. The economics can also depend on the disposal of biomass that would normally be placed in a landfill.
The growing, harvesting and processing of biomass in a water environment provides a space where there is plenty of sunlight and nutrients while not detracting from more productive alternate uses. Biomass is also generated in many everyday processes as a waste product, such as waste material from crops. In addition, biomass contributes to the removal of carbon dioxide from the atmosphere as the biomass grows. The use of biomass can be one process for recycling atmospheric carbon while producing fuels and chemical precursors. Biomass when heated at short contact times in an environment with low or no oxygen, termed pyrolysis, will generate a liquid product known as pyrolysis oil. Synonyms for pyrolysis oil include bio-oil, pyrolysis liquids, bio-crude oil, wood liquids, wood oil, liquid smoke, wood distillates, pyroligneous acid, and liquid wood
The product of the biomass pyrolysis, the pyrolysis oil, contains what is known as pyrolysis oil non-aqueous phase. Pyrolysis oil non-aqueous phase is the water insoluble portion of the pyrolysis oil. The pyrolysis oil may be processed whole, or a portion of the aqueous phase may be removed to provide a pyrolysis oil enriched in pyrolysis oil non-aqueous phase which is co-processed along with the triglycerides through deoxygenation to produce the cyclic rich portion of the fuel or fuel blending component.
The process herein involves co-processing the pyrolysis oil feedstock and the triglyceride and FFA feedstock by hydrogenation, deoxygenation (decarboxylation, decarbonylation, and/or hydrodeoxygenation) in at least a first zone and hydroisomerization and hydrocracking in at least a second zone in order to generate a gasoline range product, a diesel range product, and or an aviation range product. Simply hydrogenating and deoxygenating the renewable glyceride or FFA feedstocks in a hydrogen environment in the presence of a hydrotreating catalyst results in straight chain paraffins having chain-lengths similar to, or slightly shorter than, the fatty acid composition of the feedstock. With many feedstocks, this approach results in a fuel meeting the general specification for a diesel fuel, but not the specifications for an aviation fuel. The selective hydrocracking reaction reduces the carbon chain length to allow selectivity to aviation fuel range paraffins while minimizing lower molecular weight products. Similarly, isomerization increases the concentration of branched paraffins and thereby improve cold flow properties such as cloud point or freeze point.
The pyrolysis oil and the triglycerides are co-processed to generate an effluent comprising at least one paraffin rich component and at least one cyclic rich component. The effluent is useful as a fuel or a fuel blending component. The relative amounts of the feedstocks may be controlled so that the resulting effluent meets specific requirements of a target fuel. Other additives or components may be blended with the effluent in order to meet additional requirements of the target fuel. The target fuel may be in the boiling point ranges of gasoline, aviation, and diesel, and may be entirely derived from renewable sources. The target fuel is designed to power engines or devices that are currently distributed around the world without requiring upgrades to those engines. The target fuel may be blended with other components generated from renewable feedstocks to meet the specifications using entirely renewable feedstock derived blending components, or the target fuel may be blended with petroleum derived fuels or fuel blending components in any concentration.